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Education: Ph.D. (Kyoto University)

Research Area: Synthetic Organic Chemistry, Organometallic Chemistry and Catalysis

Phone: (65) 6513 8014

E-mail: hayashi@ntu.edu.sg


Research Interest

1) Synthetic Organic Chemistry: Selective organic synthesis catalyzed by transition metal complexes, particularly new carbon–carbon bond forming reactions

2) Organometallic Chemistry: Mechanistic understanding of catalytic reactions by characterization of key intermediates and kinetic studies

3) Catalysis: Asymmetric catalysis, development of a new type of catalytic asymmetric reactions and design of new chiral ligands.

Rhodium-Catalyzed Asymmetric Arylation, Alkenylation, and Alkynylation

Currently we are studying development of a new type of catalytic carbon-carbon bond forming reactions with high catalytic activity and high selectivity. One of the successful examples is rhodium-catalyzed asymmetric arylation, alkenylation, and alkynylation reactions. In the presence of a catalytic amount of a rhodium complex coordinated with chiral diene ligand, asymmetric addition of aryl- and alkenylboronic acids to electron deficient olefins takes place to give the corresponding addition products with high (>95% ee) enantioselectivity. The electron deficient olefins cover quinone methides and alkenyl sulfones in addition to a,ß-unsaturated carbonyl compounds. Asymmetric alkynylation was also realized with newly designed chiral diene-rhodium catalysts. Some of the published results are shown below. .

Selected Representative Publications

  1. 1. A Base Free Condition for Rhodium-Catalyzed Asymmetric Arylation Producing Stereochemically Labile a-Arylketones. Dou, X.; Lu, Y.; Hayashi, T. Angew. Chem. Int. Ed. 2016, 55, Early View.

  2. 2. Asymmetric Conjugate Alkynylation of Cyclic a,ß-Unsaturated Carbonyl Compounds with a Chiral Diene–Rhodium Catalyst. Dou, X.; Huang, Y.; Hayashi, T. Angew. Chem. Int. Ed. 2016, 55, 1133–1137.

  3. 3. Asymmetric Synthesis of Triarylmethanes by Rhodium-Catalyzed Enantioselective Arylation of Diarylmethylamines with Arylboroxines. Huang, Y.; Hayashi, T. J. Am. Chem. Soc. 2015, 137, 7556–7559 

  4. 4. Rhodium-Catalyzed Asymmetric Arylation of Allyl Sulfones under the Conditions of Isomerization into Alkenyl Sulfones. Lim, K. M.-H.; Hayashi, T.J. Am. Chem. Soc. 2015, 137, 3201–3204.

  5. 5. Nickel-Catalyzed Three-Component Domino Reactions of Aryl Grignard Reagents, Alkynes, and Aryl Halides Producing Tetrasubstituted Alkenes. Xue, F.; Zhao, J.; Hor, T. S. A.; Hayashi, T.J. Am. Chem. Soc. 2015, 137, 3189–3192.